Ionic liquids

ABSTRACT

The present invention relates to compositions of matter that are ionic liquids, the compositions comprising any of eleven cations combined with any of three fluorinated sulfonated anions. Compositions of the invention should be useful as solvents and, perhaps, as catalysts for many reactions, including aromatic electrophilic substitution, nitration, acylation, esterification, etherification, oligomerization, transesterification, isomerization and hydration.

FIELD OF INVENTION

This invention relates to compositions of matter that are useful asionic liquids.

BACKGROUND OF THE INVENTION

Ionic liquids are liquids composed of ions that are fluid around orbelow 100 degrees C. (Science (2003) 302:792-793). Ionic liquids exhibitnegligible vapor pressure, and with increasing regulatory pressure tolimit the use of traditional industrial solvents due to environmentalconsiderations such as volatile emissions and aquifer and drinking watercontamination, much research has been devoted to designing ionic liquidsthat could function as replacements for conventional solvents.

The present invention provides novel compositions comprising fluorinatedanions that are useful as ionic liquids. Fluorous ionic liquids havebeen described. For example, Merrigan, et al. (Chem. Comm. (2002)2051-2052) describe imidazole-derived ionic liquids having fluoroustails, and Wasserscheid, et al. (Green Chemistry (2002) 4:134-138)describe the synthesis of imidazolium-derived ionic liquids having abis(trifluoromethanesulfonato)amide anion. In addition, Rudyuk, et al.describe the synthesis of N-polyfluoroethyl and N-2-chlorodifluorovinylderivatives of azoles, such as imidazole, pyrazole and triazole.

SUMMARY OF THE INVENTION

In its broadest aspect, the present invention relates to a compositionof matter of the Formula Z⁺A⁻, wherein Z⁺ is a cation selected from thegroup consisting of the following eleven cations:

and A⁻ is selected from the group consisting of the following threeanions:

wherein the R-groups are defined as in the detailed description.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to novel compositions comprisingfluorinated, sulfonated anions. Compositions of the invention should beuseful as solvents and, perhaps, as catalysts for many reactions,including aromatic electrophilic substitution, nitration, acylation,esterification, etherification, oligomerization, transesterification,isomerization and hydration.

DEFINITIONS

In this disclosure, a number of terms and abbreviations are used. Thefollowing definitions are provided.

By “ionic liquid” is meant organic salts that are fluid around or below100 degrees C.

By “fluoroalkyl” is meant an alkyl group wherein at least one memberselected from the hydrogens has been replaced by fluorine. By“perfluoroalkyl” is meant an alkyl group wherein all of the hydrogenshave been replaced by fluorines.

By “alkoxy” is meant a straight-chain or branched alkyl group bound viaan oxygen atom. By “fluoroalkoxy” is meant an alkoxy group wherein atleast one member selected from the hydrogens has been replaced byfluorine. By “perfluoroalkoxy” is meant an alkoxy group wherein all ofthe hydrogens have been replaced by fluorines.

By “halogen” is meant bromine, iodine, chlorine or fluorine.

By “heteroaryl” is meant an aryl group having one or more heteroatoms.

When referring to an alkane, alkene, alkoxy, fluoroalkoxy,perfluoroalkoxy, fluoroalkyl, perfluoroalkyl, aryl or heteroaryl, theterm “optionally substituted with at least one member selected from thegroup consisting of” means that one or more hydrogens on the carbonchain may be independently substituted with one or more of at least onemember of the group. For example, substituted C₂H₅ may be, withoutlimitations, CF₂CF₃, CH₂CH₂OH or CF₂CF₂I.

The expression “C1 to Cn straight-chain or branched”, where n is aninteger defining the length of the carbon chain, is meant to indicatethat C1 and C2 are straight-chain, and C3 to Cn may be straight-chain orbranched.

The present invention relates to compositions of matter of the FormulaZ⁺A⁻, wherein Z⁺ is a cation selected from the group consisting of:

wherein R¹, R², R³, R⁴, R⁵ and R⁶ are independently selected from thegroup consisting of:

-   -   (i) H    -   (ii) halogen    -   (iii) —CH₃, —C₂H₅, or C₃ to C₂₅, preferably C₃ to C₂₀,        straight-chain, branched or cyclic alkane or alkene, optionally        substituted with at least one member selected from the group        consisting of Cl, Br, F, I, OH, NH₂ and SH;    -   (iv) —CH₃, —C₂H₅, or C₃ to C₂₅, preferably C₃ to C₂₀,        straight-chain, branched or cyclic alkane or alkene comprising        one to three heteroatoms selected from the group consisting of        O, N and S, and optionally substituted with at least one member        selected from the group consisting of Cl, Br, F, I, OH, NH₂ and        SH;    -   (v) C₆ to C₂₅ unsubstituted aryl or C₆ to C₂₅ unsubstituted        heteroaryl having one to three heteroatoms independently        selected from the group consisting of O, N and S; and    -   (vi) C₆ to C₂₅ substituted aryl or C₆ to C₂₅ substituted        heteroaryl having one to three heteroatoms independently        selected from the group consisting of O, N and S; and wherein        said substituted aryl or substituted heteroaryl has one to three        substituents independently selected from the group consisting        of:        -   (1) —CH₃, —C₂H₅, or C₃ to C₂₅, preferably C₃ to C₂₀,            straight-chain, branched or cyclic alkane or alkene,            optionally substituted with at least one member selected            from the group consisting of Cl, Br, F, I, OH, NH₂ and SH,        -   (2) OH,        -   (3) NH₂, and        -   (4) SH;            R⁷, R⁸, R⁹, and R¹⁰ are independently selected from the            group consisting of:    -   (vii) —CH₃, —C₂H₅, or C₃ to C₂₅, preferably C₃ to C₂₀,        straight-chain, branched or cyclic alkane or alkene, optionally        substituted with at least one member selected from the group        consisting of Cl, Br, F, 1, OH, NH₂ and SH;    -   (viii) —CH₃, —C₂H₅, or C₃ to C₂₅, preferably C₃ to C₂₀,        straight-chain, branched or cyclic alkane or alkene comprising        one to three heteroatoms selected from the group consisting of        O, N and S, and optionally substituted with at least one member        selected from the group consisting of Cl, Br, F, 1, OH, NH₂ and        SH;    -   (ix) C₆ to C₂₅ unsubstituted aryl or C₆ to C₂₅ unsubstituted        heteroaryl having one to three heteroatoms independently        selected from the group consisting of O, N and S; and    -   (x) C₆ to C₂₅ substituted aryl or C₆ to C₂₅ substituted        heteroaryl having one to three heteroatoms independently        selected from the group consisting of O, N and S; and wherein        said substituted aryl or substituted heteroaryl has one to three        substituents independently selected from the group consisting of        -   (1) —CH₃, —C₂H₅, or C₃ to C₂₅, preferably C₃ to C₂₀,            straight-chain, branched or cyclic alkane or alkene,            optionally substituted with at least one member selected            from the group consisting of Cl, Br, F, 1, OH, NH₂ and SH,        -   (2) OH,        -   (3) NH₂, and        -   (4) SH; and wherein            optionally at least two of R¹, R², R³, R⁴, R⁵, R⁶R⁷, R⁸, R⁹,            and R¹⁰ can together form a cyclic or bicyclic alkanyl or            alkenyl group;

and A⁻ is an anion selected from the group consisting of Formulae I, IIand III:

wherein:R¹¹ is selected from the group consisting of:

-   -   (1) halogen;    -   (2) —CH₃, —C₂H₅ or C₃ to C₁₅, preferably C₃ to C₆,        straight-chain or branched alkane or alkene, optionally        substituted with at least one member selected from the group        consisting of Cl, Br, I, OH, NH₂ and SH;    -   (3) —OCH₃, —OC₂H₅ or C₃ to C₁₅, preferably C₃ to C₆,        straight-chain or branched alkoxy, optionally substituted with        at least one member selected from the group consisting of Cl,        Br, I, OH, NH₂ and SH;    -   (4) C₁ to C₁₅, preferably C₁ to C₆, straight-chain or branched        fluoroalkyl, optionally substituted with at least one member        selected from the group consisting of Cl, Br, I, OH, NH₂ and SH;    -   (5) C₁ to C₁₅, preferably C₁ to C₆, straight-chain or branched        fluoroalkoxy, optionally substituted with at least one member        selected from the group consisting of Cl, Br, I, OH, NH₂ and SH;    -   (6) C₁ to C₁₅, preferably C₁ to C₆, straight-chain or branched        perfluoroalkyl; and    -   (7) C₁ to C₁₅, preferably C₁ to C₆, straight-chain or branched        perfluoroalkoxy;

wherein:R¹² is selected from the group consisting of:

-   -   (1) —OCH₃, —OC₂H₅ or C₃ to C₁₅, preferably C₃ to C₆,        straight-chain or branched alkoxy, optionally substituted with        at least one member selected from the group consisting of Cl,        Br, I, OH, NH₂ and SH;    -   (2) C₁ to C₁₅, preferably C₁ to C₆, straight-chain or branched        fluoroalkoxy, optionally substituted with at least one member        selected from the group consisting of Cl, Br, I, OH, NH₂ and SH;        and    -   (3) C₁ to C₁₅, preferably C₁ to C₆, straight-chain or branched        perfluoroalkoxy; and

wherein:R¹³ is selected from the group consisting of:

-   -   (1) halogen;    -   (2) —CH₃, —C₂H₅ or C₃ to C₁₅, preferably C₃ to C₆,        straight-chain or branched alkane or alkene, optionally        substituted with at least one member selected from the group        consisting of Cl, Br, I, OH, NH₂ and SH;    -   (3) —OCH₃, —OC₂H₅ or C₃ to C₁₅, preferably C₃ to C₆,        straight-chain or branched alkoxy, optionally substituted with        at least one member selected from the group consisting of Cl,        Br, I, OH, NH₂ and SH;    -   (4) C₁ to C₁₅, preferably C₁ to C₆, straight-chain or branched        fluoroalkyl, optionally substituted with at least one member        selected from the group consisting of Cl, Br, I, OH, NH₂ and SH;    -   (5) C₁ to C₁₅, preferably C₁ to C₆, straight-chain or branched        fluoroalkoxy, optionally substituted with at least one member        selected from the group consisting of Cl, Br, I, OH, NH₂ and SH;    -   (6) C₁ to C₁₅, preferably C₁ to C₆, straight-chain or branched        perfluoroalkyl; and    -   (7) C₁ to C₁₅, preferably C₁ to C₆, straight-chain or branched        perfluoroalkoxy.

In preferred embodiments of the invention, the anion is selected fromthe group consisting of 1,1,2,2-tetrafluoroethanesulfonate;2-chloro-1,1,2-trifluoroethanesulfonate;1,1,2,3,3,3-hexafluoropropanesulfonate;1,1,2-trifluoro-2-(trifluoromethoxy)ethanesulfonate;1,1,2-trifluoro-2-(pentafluoroethoxy)ethanesulfonate;2-(1,2,2,2-tetrafluoroethoxy)-1,1,2,2-tetrafluoroethanesulfonate;2-(1,1,2,2-tetrafluoroethoxy)-1,1,2,2-tetrafluoroethanesulfonate;2-(1,1,2,2-tetrafluoro-2-iodoethoxy)-1,1,2,2-tetrafluoroethanesulfonate;1,1,2,2-tetrafluoro-2-(pentafluoroethoxy)ethanesulfonate;N,N-bis(1,1,2,2-tetrafluoroethanesulfonyl)imide; andN,N-bis(1,1,2,3,3,3-hexafluoropropanesulfonyl)imide.

In one embodiment, the composition of the invention comprises a cationselected from the group consisting of pyridinium, pyridazinium,pyrimidinium, pyrazinium, imidazolium, pyrazolium, thiazolium,oxazolium, triazolium, phosphonium, ammonium as defined in all of theembodiments above; and said anion is selected from the group consistingof 1,1,2,2-tetrafluoroethanesulfonate;2-chloro-1,1,2-trifluoroethanesulfonate;1,1,2,3,3,3-hexafluoropropanesulfonate;1,1,2-trifluoro-2-(trifluoromethoxy)ethanesulfonate;1,1,2-trifluoro-2-(pentafluoroethoxy)ethanesulfonate;2-(1,2,2,2-tetrafluoroethoxy)-1,1,2,2-tetrafluoroethanesulfonate;2-(1,1,2,2-tetrafluoroethoxy)-1,1,2,2-tetrafluoroethanesulfonate;2-(1,1,2,2-tetrafluoro-2-iodoethoxy)-1,1,2,2-tetrafluoroethanesulfonate;1,1,2,2-tetrafluoro-2-(pentafluoroethoxy)ethanesulfonate;N,N-bis(1,1,2,2-tetrafluoroethanesulfonyl)imide;N,N-bis(1,1,2,3,3,3-hexafluoropropanesulfonyl)imide.

In another embodiment, the composition of the invention comprises1-butyl-2,3-dimethylimidazolium 1,1,2,2-tetrafluoroethanesulfonate,1-butyl-methylimidazolium 1,1,2,2-tetrafluoroethanesulfonate,1-ethyl-3-methylimidazolium 1,1,2,2-tetrafluoroethanesulfonate,1-ethyl-3-methylimidazolium 1,1,2,3,3,3-hexafluoropropanesulfonate,1-hexyl-3-methylimidazolium 1,1,2,2-tetrafluoroethanesulfonate,1-dodecyl-3-methylimidazolium 1,1,2,2-tetrafluoroethanesulfonate,1-hexadecyl-3-methylimidazolium 1,1,2,2-tetrafluoroethanesulfonate,1-octadecyl-3-methylimidazolium 1,1,2,2-tetrafluoroethanesulfonate,N-(1,1,2,2-tetrafluoroethyl)propylimidazole1,1,2,2-tetrafluoroethanesulfonate,N-(1,1,2,2-tetrafluoroethyl)ethylperfluorohexylimidazole1,1,2,2-tetrafluoroethanesulfonate, 1-butyl-3-methylimidazolium1,1,2,3,3,3-hexafluoropropanesulfonate, 1-butyl-3-methylimidazolium1,1,2-trifluoro-2-(trifluoromethoxy)ethanesulfonate,1-butyl-3-methylimidazolium1,1,2-trifluoro-2-(perfluoroethoxy)ethanesulfonate,tetradecyl(tri-n-hexyl)phosphonium1,1,2-trifluoro-2-(perfluoroethoxy)ethanesulfonate,tetradecyl(tri-n-butyl)phosphonium1,1,2,3,3,3-hexafluoropropanesulfonate,tetradecyl(tri-n-hexyl)phosphonium1,1,2-trifluoro-2-(trifluoromethoxy)ethanesulfonate,1-ethyl-3-methylimidazolium1,1,2,2-tetrafluoro-2-(pentafluoroethoxy)sulfonate,(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)-trioctylphosphonium1,1,2,2-tetrafluoroethanesulfonate,1-methyl-3-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)imidazolium1,1,2,2-tetrafluoroethanesulfonate, or tetra-n-butylphosphonium1,1,2-trifluoro-2-(perfluoroethoxy)ethanesulfonate.

Cations of the invention are available commercially, or may besynthesized by methods known to those skilled in the art. Thefluoroalkyl sulfonate anions may be synthesized from perfluorinatedterminal olefins or perfluorinated vinyl ethers generally according tothe method of Koshar, et al. (J. Am. Chem. Soc. (1953) 75:4595-4596); inone embodiment, sulfite and bisulfite are used as the buffer in place ofbisulfite and borax, and in another embodiment, the reaction is carriedin the absence of a radical initiator.1,1,2,2-Tetrafluoroethanesulfonate,1,1,2,3,3,3-hexafluoropropanesulfonate,1,1,2-trifluoro-2-(trifluoromethoxy)ethanesulfonate, and1,1,2-trifluoro-2-(pentafluoroethoxy)ethanesulfonate may be synthesizedaccording to Koshar, et al. (supra), with modifications. Preferredmodifications include using a mixture of sulfite and bisulfite as thebuffer, freeze drying or spray drying to isolate the crude1,1,2,2-tetrafluoroethanesulfonate and1,1,2,3,3,3-hexafluoropropanesulfonate products from the aqueousreaction mixture, using acetone to extract the crude1,1,2,2-tetrafluoroethanesulfonate and1,1,2,3,3,3-hexafluoropropanesulfonate salts, and crystallizing1,1,2-trifluoro-2-(trifluoromethoxy)ethanesulfonate and1,1,2-trifluoro-2-(pentafluoroethoxy)ethanesulfonate from the reactionmixture by cooling.

General Procedure for Synthesizing Ionic Liquids that are not Misciblewith Water:

Solution #1 is made by dissolving a known amount of the halide salt ofthe cation in deionized water. This may involve heating to ensure totaldissolution. Solution #2 is made by dissolving an approximatelyequimolar amount (relative to the cation) of the potassium or sodiumsalt of the anion in deionized water. This may also involve heating toensure total dissolution. Although it is not necessary to use equimolarquantities of the cation and anion, a 1:1 equimolar ratio minimizes theimpurities obtained by the reaction. The two aqueous solutions (#1 and#2) are mixed and stirred at a temperature that optimizes the separationof the desired product phase as either an oil or a solid on the bottomof the flask. In one embodiment, the aqueous solutions are mixed andstirred at room temperature, however the optimal temperature may behigher or lower based on the conditions necessary to achieve optimalproduct separation. The water layer is separated, and the product iswashed several times with deionized water to remove chloride or bromideimpurities. An additional base wash may help to remove acidicimpurities. The product is then diluted with an appropriate organicsolvent (chloroform, methylene chloride, etc.) and dried over anhydrousmagnesium sulfate or other preferred drying agent. The appropriateorganic solvent is one that is miscible with the ionic liquid and thatcan be dried. The drying agent is removed by suction filtration and theorganic solvent is removed in vacuo. High vacuum is applied for severalhours or until residual water is removed. The final product is usuallyin the form of a liquid.

General Procedure for the Synthesis of Ionic Liquids that are Misciblewith Water:

Solution #1 is made by dissolving a known amount of the halide salt ofthe cation in an appropriate solvent. This may involve heating to ensuretotal dissolution. Preferably the solvent is one in which the cation andanion are miscible, and in which the salts formed by the reaction areminimally miscible; in addition, the appropriate solvent is preferablyone that has a relatively low boiling point such that the solvent can beeasily removed after the reaction. Appropriate solvents include, but arenot limited to, high purity dry acetone, alcohols such as methanol andethanol, and acetonitrile. Solution #2 is made by dissolving anequimolar amount (relative to the cation) of the salt (generallypotassium or sodium) of the anion in an appropriate solvent, typicallythe same as that used for the cation. This may also involve heating toensure total dissolution. The two solutions (#1 and #2) are mixed andstirred under conditions that result in approximately completeprecipitation of the halide salt byproduct (generally potassium halideor sodium halide); in one embodiment of the invention, the solutions aremixed and stirred at approximately room temperature for about 4-12hours. The halide salt is removed by suction filtration through anacetone/celite pad, and color can be reduced through the use ofdecolorizing carbon as is known to those skilled in the art. The solventis removed in vacuo and then high vacuum is applied for several hours oruntil residual water is removed. The final product is usually in theform of a liquid.

Compositions (ionic liquids) of the present invention can be utilized inone phase systems or multiple phase systems as solvents or, perhaps, ascatalysts. The physical and chemical properties of the compositions ofthe present invention can be specifically selected by choice of theappropriate cation and anion. For example, increasing the chain lengthof one or more alkyl chains of the cation will affect properties such asthe melting point, hydrophilicity/lipophilicity, density and salvationstrength of the ionic liquid. Choice of the anion can affect, forexample, the melting point, the water solubility and the acidity andcoordination properties of the composition. Effects of cation and anionon the physical and chemical properties of ionic liquids are known tothose skilled in the art and are reviewed in detail by Wasserscheid andKeim (Angew. Chem. Int. Ed. (2000) 39:3772-3789) and Sheldon (Chem.Commun. (2001) 2399-2407).

Preparation of Polytrimethylene Ether Glycol

Compositions of the present invention are useful for the polymerizationof 1,3-propanediol. To prepare polytrimethylene ether glycol,1,3-propanediol is contacted with at least one polycondensation catalystand at least one ionic liquid of the invention to form a polyether phasecomprising polytrimethylene ether glycol and an ionic liquid phase. Thepolyether phase is then separated from the ionic liquid phase.

The 1,3-propanediol may be obtained commercially or by any of thevarious chemical routes or by biochemical transformation routes wellknown to those skilled in the art.

The temperature of the process is preferably controlled to achieve highyields of desired molecular weight and a minimum of color formation. Thepolycondensation reaction is preferably carried out at a temperature offrom about 120 degrees C. to about 250 degrees C. In one embodiment, thetemperature is from about 120 degrees C. to about 210 degrees C.; inanother embodiment the temperature is from about 120 degrees C. to about180 degrees C.; in still another embodiment, the temperature is fromabout 140 degrees C. to about 180 degrees C.

The polycondensation may be carried out under an inert atmosphere, suchas nitrogen or argon. In another embodiment, the polycondensation iscarried out at a pressure of less than about 100 KPa; in additionalembodiments the reaction is carried out at a pressure of less than about67 KPa, preferably less than about 33 KPa.

The time for the reaction will depend on many factors, such as thereactants, reaction conditions and reactor. One skilled in the art willknow to adjust the time for the reaction to achieve high yields ofpolytrimethylene ether glycol (or copolymers thereof) of the desiredmolecular weight.

The at least one polycondensation catalyst is a homogeneous acidcatalyst. In one embodiment of the invention, suitable homogeneous acidcatalysts are those having a pKa of less than about 4; in anotherembodiment, suitable homogeneous acid catalysts are those having a pKaof less than about 2.

In one embodiment, the at least one polycondensation catalyst is ahomogeneous acid catalyst selected from the group consisting ofinorganic acids, organic sulfonic acids, heteropolyacids, fluoroalkylsulfonic acids, metal sulfonates, metal trifluoroacetates, compoundsthereof and combinations thereof. In yet another embodiment, the atleast one polycondensation catalyst is a homogeneous acid catalystselected from the group consisting of sulfuric acid, fluorosulfonicacid, phosphorous acid, p-toluenesulfonic acid, benzenesulfonic acid,phosphotungstic acid, phosphomolybdic acid, trifluoromethanesulfonicacid, nonafluorobutanesulfonic acid, 1,1,2,2-tetrafluoroethanesulfonicacid, 1,1,2,3,3,3-hexafluoropropanesulfonic acid, bismuth triflate,yttrium triflate, ytterbium triflate, neodymium triflate, lanthanumtriflate, scandium triflate, and zirconium triflate. The catalyst isused at a concentration of from about 0.1% to about 20% by weight of the1,3-propanediol reactant.

The polycondensation reaction may be carried out as a batch orcontinuous process. Reactor configurations, as well as a continuousprocess for polycondensation of 1,3-propanediol reactant, are describedin U.S. Pat. No. 6,720,459, Column 5, line 49 through Column 9, line 26,and FIGS. 1 through 6.

An advantage to the use of at least one ionic liquid in this reaction isthat the reaction product comprises a polyether phase comprisingpolytrimethylene ether glycol and an ionic liquid phase that comprisesthe acid catalyst. Thus the polytrimethylene ether glycol product orproducts in the polyether phase is/are easily recoverable from the acidcatalyst by, for example, decantation. In a preferred embodiment, theacid catalyst and the at least one ionic liquid are recycled and used insubsequent reactions.

General Materials and Methods

The following abbreviations are used:

Nuclear magnetic resonance is abbreviated NMR; gas chromatography isabbreviated GC; gas chromatography-mass spectrometry is abbreviatedGC-MS; thin layer chromatography is abbreviated TLC; thermogravimetricanalysis (using a Universal V3.9A TA instrument analyzer (TAInstruments, Inc., Newcastle, Del.)) is abbreviated TGA. Centigrade isabbreviated C, mega Pascal is abbreviated MPa, gram is abbreviated g,kilogram is abbreviated Kg, milliliter(s) is abbreviated ml(s), hour isabbreviated hr; weight percent is abbreviated wt %; milliequivalents isabbreviated meq; melting point is abbreviated Mp; differential scanningcalorimetry is abbreviated DSC.

1-Butyl-2,3-dimethylimidazolium chloride, 1-hexyl-3-methylimidazoliumchloride, 1-dodecyl-3-methylimidazolium chloride, 1-hexadecyl-3-methylimidazolium chloride, 1-octadecyl-3-methylimidazolium chloride,imidazole, tetrahydrofuran, iodopropane, acetonitrile,iodoperfluorohexane, toluene, 1,3-propanediol, oleum (20% SO₃), sodiumsulfite (Na₂SO₃, 98%), and acetone were obtained from Acros (Hampton,N.H.). Potassium metabisulfite (K₂S₂O₅, 99%), was obtained fromMallinckrodt Laboratory Chemicals (Phillipsburg, N.J.). Potassiumsulfite hydrate (KHSO₃.xH₂O, 95%), sodium bisulfite (NaHSO₃), sodiumcarbonate, magnesium sulfate, ethyl ether,1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-8-iodooctane, trioctyl phosphineand 1-ethyl-3-methylimidazolium chloride (98%) were obtained fromAldrich (St. Louis, Mo.). Sulfuric acid and methylene chloride wereobtained from EMD Chemicals, Inc. (Gibbstown, N.J.).Perfluoro(ethylvinyl ether), perfluoro(methylvinyl ether),hexafluoropropene and tetrafluoroethylene were obtained from DuPontFluoroproducts (Wilmington, Del.). 1-Butyl-methylimidazolium chloridewas obtained from Fluka (Sigma-Aldrich, St. Louis, Mo.).Tetra-n-butylphosphonium bromide and tetradecyl(tri-n-hexyl)phosphoniumchloride were obtained from Cytec (Canada Inc., Niagara Falls, Ontario,Canada). 1,1,2,2-Tetrafluoro-2-(pentafluoroethoxy)sulfonate was obtainedfrom SynQuest Laboratories, Inc. (Alachua, Fla.).

Preparation of Formula I Anions not Generally Available Commercially

(A) Synthesis of potassium 1,1,2,2-tetrafluoroethanesulfonate (TFES-K)([HCF₂CF₂SO₃]⁻)

A 1-gallon Hastelloy® C276 reaction vessel was charged with a solutionof potassium sulfite hydrate (176 g, 1.0 mol), potassium metabisulfite(610 g, 2.8 mol) and deionized water (2000 ml). The pH of this solutionwas 5.8. The vessel was cooled to 18 degrees C., evacuated to 0.10 MPa,and purged with nitrogen. The evacuate/purge cycle was repeated two moretimes. To the vessel was then added tetrafluoroethylene (TFE, 66 g), andit was heated to 100 degrees C. at which time the inside pressure was1.14 MPa. The reaction temperature was increased to 125 degrees C. andkept there for 3 hr. As the TFE pressure decreased due to the reaction,more TFE was added in small aliquots (20-30 g each) to maintainoperating pressure roughly between 1.14 and 1.48 MPa. Once 500 g (5.0mol) of TFE had been fed after the initial 66 g precharge, the vesselwas vented and cooled to 25 degrees C. The pH of the clear light yellowreaction solution was 10-11. This solution was buffered to pH 7 throughthe addition of potassium metabisulfite (16 g).

The water was removed in vacuo on a rotary evaporator to produce a wetsolid. The solid was then placed in a freeze dryer (Virtis Freezemobile35xl; Gardiner, N.Y.) for 72 hr to reduce the water content toapproximately 1.5 wt % (1387 g crude material). The theoretical mass oftotal solids was 1351 g. The mass balance was very close to ideal andthe isolated solid had slightly higher mass due to moisture. This addedfreeze drying step had the advantage of producing a free-flowing whitepowder whereas treatment in a vacuum oven resulted in a soapy solid cakethat was very difficult to remove and had to be chipped and broken outof the flask.

The crude TFES-K can be further purified and isolated by extraction withreagent grade acetone, filtration, and drying.

¹⁹F NMR (D₂O) δ −122.0 (dt, J_(FH)=6 Hz, J_(FF)=6 Hz, 2F); −136.1 (dt,J_(FH)=53 Hz, 2F).

¹H NMR (D₂O) δ 6.4 (tt, J_(FH)=53 Hz, J_(FH)=6 Hz, 1H).

% Water by Karl-Fisher titration: 580 ppm.

Analytical calculation for C₂HO₃F₄SK: C, 10.9: H, 0.5: N, 0.0

Experimental results: C, 11.1: H, 0.7: N, 0.2.

Mp (DSC): 242 degrees C.

TGA (air): 10% wt. loss @ 367 degrees C., 50% wt. loss @ 375 degrees C.

TGA (N₂): 10% wt. loss @ 363 degrees C., 50% wt. loss @ 375 degrees C.

(B) Synthesis ofpotassium-1,1,2-trifluoro-2-(perfluoroethoxy)ethanesulfonate (TPES-K)

A 1-gallon Hastelloy® C276 reaction vessel was charged with a solutionof potassium sulfite hydrate (88 g, 0.56 mol), potassium metabisulfite(340 g, 1.53 mol) and deionized water (2000 ml). The vessel was cooledto 7 degrees C., evacuated to 0.05 MPa, and purged with nitrogen. Theevacuate/purge cycle was repeated two more times. To the vessel was thenadded perfluoro(ethylvinyl ether) (PEVE, 600 g, 2.78 mol), and it washeated to 125 degrees C. at which time the inside pressure was 2.31 MPa.The reaction temperature was maintained at 125 degrees C. for 10 hr. Thepressure dropped to 0.26 MPa at which point the vessel was vented andcooled to 25 degrees C. The crude reaction product was a whitecrystalline precipitate with a colorless aqueous layer (pH=7) above it.

The ¹⁹F NMR spectrum of the white solid showed pure desired product,while the spectrum of the aqueous layer showed a small but detectableamount of a fluorinated impurity. The desired isomer is less soluble inwater so it precipitated in isomerically pure form.

The product slurry was suction filtered through a fritted glass funnel,and the wet cake was dried in a vacuum oven (60 degrees C., 0.01 MPa)for 48 hr. The product was obtained as off-white crystals (904 g, 97%yield).

¹⁹F NMR (D₂O) δ −86.5 (s, 3F); −89.2, −91.3 (subsplit ABq, J_(FF)=147Hz, 2F);

−119.3, −121.2 (subsplit ABq, J_(FF)=258 Hz, 2F); −144.3 (dm, J_(FH)=53Hz, 1F).

¹H NMR (D₂O) δ 6.7 (dm, J_(FH)=53 Hz, 1H).

Mp (DSC) 263 degrees C.

Analytical calculation for C₄HO₄F₈SK: C, 14.3: H, 0.3 Experimentalresults: C, 14.1: H, 0.3.

TGA (air): 10% wt. loss @ 359 degrees C., 50% wt. loss @ 367 degrees C.

TGA (N₂): 10% wt. loss @ 362 degrees C., 50% wt. loss @ 374 degrees C.

(C) Synthesis ofpotassium-1,1,2-trifluoro-2-(trifluoromethoxy)ethanesulfonate (TTES-K)

A 1-gallon Hastelloy® C276 reaction vessel was charged with a solutionof potassium sulfite hydrate (114 g, 0.72 mol), potassium metabisulfite(440 g, 1.98 mol) and deionized water (2000 ml). The pH of this solutionwas 5.8. The vessel was cooled to −35 degrees C., evacuated to 0.08 MPa,and purged with nitrogen. The evacuate/purge cycle was repeated two moretimes. To the vessel was then added perfluoro(methylvinyl ether) (PMVE,600 g, 3.61 mol) and it was heated to 125 degrees C. at which time theinside pressure was 3.29 MPa. The reaction temperature was maintained at125 degrees C. for 6 hr. The pressure dropped to 0.27 MPa at which pointthe vessel was vented and cooled to 25 degrees C. Once cooled, a whitecrystalline precipitate of the desired product formed leaving acolorless clear aqueous solution above it (pH=7).

The ¹⁹F NMR spectrum of the white solid showed pure desired product,while the spectrum of the aqueous layer showed a small but detectableamount of a fluorinated impurity.

The solution was suction filtered through a fritted glass funnel for 6hr to remove most of the water. The wet cake was then dried in a vacuumoven at 0.01 MPa and 50 degrees C. for 48 hr. This gave 854 g (83%yield) of a white powder. The final product was isomerically pure (by¹⁹F and ¹H NMR) since the undesired isomer remained in the water duringfiltration.

¹⁹F NMR (D₂O) δ −59.9 (d, J_(FH)=4 Hz, 3F); −119.6, −120.2 (subsplitABq, J=260 Hz, 2F); −144.9 (dm, J_(FH)=53 Hz, 1F).

¹H NMR (D₂O) δ 6.6 (dm, J_(FH)=53 Hz, 1H).

% Water by Karl-Fisher titration: 71 ppm.

Analytical calculation for C₃HF₆SO₄K: C, 12.6: H, 0.4: N, 0.0

Experimental results: C, 12.6: H, 0.0: N, 0.1.

Mp (DSC) 257 degrees C.

TGA (air): 10% wt. loss @ 343 degrees C., 50% wt. loss @ 358 degrees C.

TGA (N₂): 10% wt. loss @ 341 degrees C., 50% wt. loss @ 357 degrees C.

(D) Synthesis of sodium 1,1,2,3,3,3-hexafluoropropanesulfonate (HFPS-Na)

A 1-gallon Hastelloy® C reaction vessel was charged with a solution ofanhydrous sodium sulfite (25 g, 0.20 mol), sodium bisulfite 73 g, (0.70mol) and of deionized water (400 ml). The pH of this solution was 5.7.The vessel was cooled to 4 degrees C., evacuated to 0.08 MPa, and thencharged with hexafluoropropene (HFP, 120 g, 0.8 mol, 0.43 MPa). Thevessel was heated with agitation to 120 degrees C. and kept there for 3hr. The pressure rose to a maximum of 1.83 MPa and then dropped down to0.27 MPa within 30 minutes. At the end, the vessel was cooled and theremaining HFP was vented, and the reactor was purged with nitrogen. Thefinal solution had a pH of 7.3.

The water was removed in vacuo on a rotary evaporator to produce a wetsolid. The solid was then placed in a vacuum oven (0.02 MPa, 140 degreesC., 48 hr) to produce 219 g of white solid which contained approximately1 wt % water. The theoretical mass of total solids was 217 g.

The crude HFPS-Na can be further purified and isolated by extractionwith reagent grade acetone, filtration, and drying.

¹⁹F NMR (D₂O) δ −74.5 (m, 3F); −113.1, −120.4 (ABq, J=264 Hz, 2F);−211.6 (dm, 1F).

¹H NMR (D₂O) δ 5.8 (dm, J_(FH)=43 Hz, 1H).

Mp (DSC) 126 degrees C.

TGA (air): 10% wt. loss @ 326 degrees C., 50% wt. loss @ 446 degrees C.

TGA (N₂): 10% wt. loss @ 322 degrees C., 50% wt. loss @ 449 degrees C.

Examples 1-19 Exemplify the Synthesis of Compositions of the InventionExample 1 Synthesis of 1-butyl-2,3-dimethylimidazolium1,1,2,2-tetrafluoroethanesulfonate (Cation, imidazolium; Anion, Formula1)

1-Butyl-2,3-dimethylimidazolium chloride (22.8 g, 0.121 moles) was mixedwith reagent-grade acetone (250 ml) in a large round-bottomed flask andstirred vigorously. Potassium 1,1,2,2-tetrafluoroethanesulfonate(TFES-K, 26.6 g, 0.121 moles) was added to reagent grade acetone (250ml) in a separate round-bottomed flask, and this solution was carefullyadded to the 1-butyl-2,3-dimethylimidazolium chloride solution. Thelarge flask was lowered into an oil bath and heated at 60 degrees C.under reflux for 10 hours. The reaction mixture was then filtered usinga large frit glass funnel to remove the white KCl precipitate formed,and the filtrate was placed on a rotary evaporator for 4 hours to removethe acetone. The product was isolated and dried under vacuum at 150degrees C. for 2 days.

¹H NMR (DMSO-d₆): δ 0.9 (t, 3H); 1.3 (m, 2H); 1.7 (m, 2H); 2.6 (s, 3H);3.8 (s, 3H); 4.1 (t, 2H); 6.4 (tt, 1H); 7.58 (s, 1H); 7.62 (s, 1H).

% Water by Karl-Fischer titration: 0.06%.

TGA (air): 10% wt. loss @ 375 degrees C., 50% wt. loss @ 415 degrees C.

TGA (N₂): 10% wt. loss @ 395 degrees C., 50% wt. loss @ 425 degrees C.

The reaction scheme is shown below:

Example 2 Synthesis of 1-butyl-3-methylimidazolium1,1,2,2-tetrafluoroethanesulfonate (Bmim-TFES) (Cation, imidazolium;Anion, Formula 1)

1-Butyl-3-methylimidazolium chloride (60.0 g) and high purity dryacetone (>99.5%, 300 ml) were combined in a 1 liter flask and warmed toreflux with magnetic stirring until the solid completely dissolved. Atroom temperature in a separate 1 liter flask,potassium-1,1,2,2-tetrafluoroethanesulfonte (TFES-K, 75.6 g) wasdissolved in high purity dry acetone (500 ml). These two solutions werecombined at room temperature and allowed to stir magnetically for 2 hrunder positive nitrogen pressure. The stirring was stopped and the KClprecipitate was allowed to settle, then removed by suction filtrationthrough a fritted glass funnel with a celite pad. The acetone wasremoved in vacuo to give a yellow oil. The oil was further purified bydiluting with high purity acetone (100 ml) and stirring withdecolorizing carbon (5 g). The mixture was again suction filtered andthe acetone removed in vacuo to give a colorless oil. This was furtherdried at 4 Pa and 25 degrees C. for 6 hr to provide 83.6 g of product.

¹⁹F NMR (DMSO-d₆) δ −124.7 (dt, J=6 Hz, J=8 Hz, 2F); −136.8 (dt, J=53Hz, 2F).

¹H NMR (DMSO-d₆) δ 0.9 (t, J=7.4 Hz, 3H); 1.3 (m, 2H); 1.8 (m, 2H); 3.9(s, 3H); 4.2 (t, J=7 Hz, 2H); 6.3 (dt, J=53 Hz, J=6 Hz, 1H); 7.4 (s,1H); 7.5 (s, 1H); 8.7 (s, 1H).

% Water by Karl-Fisher titration: 0.14%.

Analytical calculation for C₉H₁₂F₆N₂O₃S: C, 37.6: H, 4.7: N, 8.8.

Experimental Results: C, 37.6: H, 4.6: N, 8.7.

TGA (air): 10% wt. loss @ 380 degrees C., 50% wt. loss @ 420 degrees C.

TGA (N₂): 10% wt. loss @ 375 degrees C., 50% wt. loss @ 422 degrees C.

Example 3 Synthesis of 1-ethyl-3-methylimidazolium1,1,2,2-tetrafluoroethanesulfonate (Emim-TFES) (Cation, imidazolium;Anion, Formula 1)

To a 500 ml round bottom flask was added 1-ethyl-3-methylimidazoliumchloride (Emim-Cl, 98%, 61.0 g) and reagent grade acetone (500 ml). Themixture was gently warmed (50 degrees C.) until almost all of theEmim-Cl dissolved. To a separate 500 ml flask was added potassium1,1,2,2-tetrafluoroethanesulfonate (TFES-K, 90.2 g) along with reagentgrade acetone (350 ml). This second mixture was stirred magnetically at24 degrees C. until all of the TFES-K dissolved.

These solutions were combined in a 1 liter flask producing a milky whitesuspension. The mixture was stirred at 24 degrees C. for 24 hrs. The KClprecipitate was then allowed to settle leaving a clear green solutionabove it.

The reaction mixture was filtered once through a celite/acetone pad andagain through a fritted glass funnel to remove the KCl. The acetone wasremoved in vacuo first on a rotovap and then on a high vacuum line (4Pa, 25 degrees C.) for 2 hr. The product was a viscous light yellow oil(76.0 g, 64% yield).

¹⁹F NMR (DMSO-d₆) δ −124.7 (dt, J_(FH)=6 Hz, J_(FF)=6 Hz, 2F); −138.4(dt, J_(FH)=53 Hz, 2F).

¹H NMR (DMSO-d₆) δ 1.3 (t, J=7.3 Hz, 3H); 3.7 (s, 3H); 4.0 (q, J=7.3 Hz,2H);

6.1 (tt, J_(FH)=53 Hz, J_(FH)=6 Hz, 1H); 7.2 (s, 1H); 7.3 (s, 1H); 8.5(s, 1H).

% Water by Karl-Fisher titration: 0.18%.

Analytical calculation for C₈H₁₂N₂O₃F₄S: C, 32.9: H, 4.1: N, 9.6. Found:

C, 33.3: H, 3.7: N, 9.6. Mp 45-46 degrees C.

TGA (air): 10% wt. loss @ 379 degrees C., 50% wt. loss @ 420 degrees C.

TGA (N₂): 10% wt. loss @ 378 degrees C., 50% wt. loss @ 418 degrees C.

The reaction scheme is shown below:

Example 4 Synthesis of 1-ethyl-3-methylimidazolium1,1,2,3,3,3-hexafluoropropanesulfonate (Emim-HFPS) (Cation, imidazolium;Anion, Formula 1)

To a 1 l round bottom flask was added 1-ethyl-3-methylimidazoliumchloride (Emim-Cl, 98%, 50.5 g) and reagent grade acetone (400 ml). Themixture was gently warmed (50 degrees C.) until almost all of theEmim-Cl dissolved. To a separate 500 ml flask was added potassium1,1,2,3,3,3-hexafluoropropanesulfonate (HFPS-K, 92.2 g) along withreagent grade acetone (300 ml). This second mixture was stirredmagnetically at room temperature until all of the HFPS-K dissolved.

These solutions were combined and stirred under positive N₂ pressure at26 degrees C. for 12 hr producing a milky white suspension. The KClprecipitate was allowed to settle overnight leaving a clear yellowsolution above it.

The reaction mixture was filtered once through a celite/acetone pad andagain through a fritted glass funnel. The acetone was removed in vacuofirst on a rotovap and then on a high vacuum line (4 Pa, 25 degrees C.)for 2 hr. The product was a viscous light yellow oil (103.8 g, 89%yield).

¹⁹F NMR (DMSO-d₆) δ −73.8 (s, 3F); −114.5, −121.0 (ABq, J=258 Hz, 2F);−210.6 (m, 1F, J_(HF)=41.5 Hz).

¹H NMR (DMSO-d₆) δ 1.4 (t, J=7.3 Hz, 3H); 3.9 (s, 3H); 4.2 (q, J=7.3 Hz,2H,);

5.8 (m, J_(HF)=41.5 Hz, 1H,); 7.7 (s, 1H); 7.8 (s, 1H); 9.1 (s, 1H).

% Water by Karl-Fisher titration: 0.12%.

Analytical calculation for C₉H₁₂N₂O₃F₆S: C, 31.5: H, 3.5: N, 8.2.

Experimental Results: C, 30.9: H, 3.3: N, 7.8.

TGA (air): 10% wt. loss @ 342 degrees C., 50% wt. loss @ 373 degrees C.

TGA (N₂): 10% wt. loss @ 341 degrees C., 50% wt. loss @ 374 degrees C.

The reaction scheme is shown below:

Example 5 Synthesis of 1-hexyl-3-methylimidazolium1,1,2,2-tetrafluoroethanesulfonate (Cation, imidazolium; Anion, Formula1)

1-Hexyl-3-methylimidazolium chloride (10 g, 0.0493 moles) was mixed withreagent-grade acetone (100 ml) in a large round-bottomed flask andstirred vigorously under a nitrogen blanket. Potassium1,1,2,2-tetrafluoroethane sulfonate (TFES-K, 10 g, 0.0455 moles) wasadded to reagent grade acetone (100 ml) in a separate round-bottomedflask, and this solution was carefully added to the1-hexyl-3-methylimidazolium chloride/acetone mixture. The mixture wasleft to stir overnight. The reaction mixture was then filtered using alarge frit glass funnel to remove the white KCl precipitate formed, andthe filtrate was placed on a rotary evaporator for 4 hours to remove theacetone.

Appearance: pale yellow, viscous liquid at room temperature.

¹H NMR (DMSO-d₆): δ 0.9 (t, 3H); 1.3 (m, 6H); 1.8 (m, 2H); 3.9 (s, 3H);4.2 (t, 2H); 6.4 (tt, 1H); 7.7 (s, 1H); 7.8 (s, 1H); 9.1 (s, 1H).

% Water by Karl-Fischer titration: 0.03%

TGA (air): 10% wt. loss @ 365 degrees C., 50% wt. loss @ 410 degrees C.

TGA (N₂): 10% wt. loss @ 370 degrees C., 50% wt. loss @ 415 degrees C.

The reaction scheme is shown below:

Example 6 Synthesis of 1-dodecyl-3-methylimidazolium1,1,2,2-tetrafluoroethanesulfonate (Cation, imidazolium; Anion, Formula1)

1-Dodecyl-3-methylimidazolium chloride (34.16 g, 0.119 moles) waspartially dissolved in reagent-grade acetone (400 ml) in a largeround-bottomed flask and stirred vigorously. Potassium1,1,2,2-tetrafluoroethanesulfonate (TFES-K, 26.24 g, 0.119 moles) wasadded to reagent grade acetone (400 ml) in a separate round-bottomedflask, and this solution was carefully added to the1-dodecyl-3-methylimidazolium chloride solution. The reaction mixturewas heated at 60 degrees C. under reflux for approximately 16 hours. Thereaction mixture was then filtered using a large frit glass funnel toremove the white KCl precipitate formed, and the filtrate was placed ona rotary evaporator for 4 hours to remove the acetone.

¹H NMR (CD₃CN): δ 0.9 (t, 3H); 1.3 (m. 18H); 1.8 (m, 2H); 3.9 (s, 3H);4.2 (t, 2H); 6.4 (tt, 1H); 7.7 (s, 1H); 7.8 (s, 1H); 9.1 (s, 1H).

¹⁹F NMR (CD₃CN): δ −125.3 (m, 2F); −137 (dt, 2F).

% Water by Karl-Fischer titration: 0.24%

TGA (air): 10% wt. loss @ 370 degrees C., 50% wt. loss @ 410 degrees C.

TGA (N₂): 10% wt. loss @ 375 degrees C., 50% wt. loss @ 410 degrees C.

The reaction scheme is shown below:

Example 7 Synthesis of 1-hexadecyl-3-methylimidazolium1,1,2,2-tetrafluoroethanesulfonate (Cation, imidazolium; Anion, Formula1)

1-Hexadecyl-3-methylimidazolium chloride (17.0 g, 0.0496 moles) waspartially dissolved in reagent-grade acetone (100 ml) in a largeround-bottomed flask and stirred vigorously. Potassium1,1,2,2-tetrafluoroethanesulfonate (TFES-K, 10.9 g, 0.0495 moles) wasadded to reagent grade acetone (100 ml) in a separate round-bottomedflask, and this solution was carefully added to the1-hexadecyl-3-methylimidazolium chloride solution. The reaction mixturewas heated at 60 degrees C. under reflux for approximately 16 hours. Thereaction mixture was then filtered using a large frit glass funnel toremove the white KCl precipitate formed, and the filtrate was placed ona rotary evaporator for 4 hours to remove the acetone.

Appearance: white solid at room temperature.

¹H NMR (CD₃CN): δ 0.9 (t, 3H); 1.3 (m, 26H); 1.9 (m, 2H); 3.9 (s, 3H);4.2 (t, 2H); 6.3 (tt, 1H); 7.4 (s, 1H); 7.4 (s, 1H); 8.6 (s, 1H).

¹⁹F NMR (CD₃CN): δ −125.2 (m, 2F); −136.9 (dt, 2F).

% Water by Karl-Fischer titration: 200 ppm.

TGA (air): 10% wt. loss @ 360 degrees C., 50% wt. loss @ 395 degrees C.

TGA (N₂): 10% wt. loss @ 370 degrees C., 50% wt. loss @ 400 degrees C.

The reaction scheme is shown below:

Example 8 Synthesis of 1-octadecyl-3-methylimidazolium1,1,2,2-tetrafluoroethanesulfonate (Cation, imidazolium; Anion, Formula1)

1-Octadecyl-3-methylimidazolium chloride (17.0 g, 0.0458 moles) waspartially dissolved in reagent-grade acetone (200 ml) in a largeround-bottomed flask and stirred vigorously. Potassium1,1,2,2-tetrafluoroethanesulfonate (TFES-K, 10.1 g, 0.0459 moles), wasadded to reagent grade acetone (200 ml) in a separate round-bottomedflask, and this solution was carefully added to the1-octadecyl-3-methylimidazolium chloride solution. The reaction mixturewas heated at 60 degrees C. under reflux for approximately 16 hours. Thereaction mixture was then filtered using a large frit glass funnel toremove the white KCl precipitate formed, and the filtrate was placed ona rotary evaporator for 4 hours to remove the acetone.

¹H NMR (CD₃CN): δ 0.9 (t, 3H); 1.3 (m, 30H); 1.9 (m, 2H); 3.9 (s, 3H);4.1 (t, 2H); 6.3 (tt, 1H); 7.4 (s, 1H); 7.4 (s, 1H); 8.5 (s, 1H).

¹⁹F NMR (CD₃CN): δ −125.3 (m, 2F); −136.9 (dt, 2F).

% Water by Karl-Fischer titration: 0.03%.

TGA (air): 10% wt. loss @ 360 degrees C., 50% wt. loss @ 400 degrees C.

TGA (N₂): 10% wt. loss @ 365 degrees C., 50% wt. loss @ 405 degrees C.

The reaction scheme is shown below:

Example 9 Synthesis of 1-propyl-3-(1,1,2,2-TFES) imidazolium1,1,2,2-tetrafluoroethanesulfonate (Cation, imidazolium; Anion, Formula1)

Imidazole (19.2 g) was added to of tetrahydrofuran (80 mls). A glassshaker tube reaction vessel was filled with the THF-containing imidazolesolution. The vessel was cooled to 18° C., evacuated to 0.08 MPa, andpurged with nitrogen. The evacuate/purge cycle was repeated two moretimes. Tetrafluoroethylene (TFE, 5 g) was then added to the vessel, andit was heated to 100 degrees C., at which time the inside pressure wasabout 0.72 MPa. As the TFE pressure decreased due to the reaction, moreTFE was added in small aliquots (5 g each) to maintain operatingpressure roughly between 0.34 MPa and 0.86 MPa. Once 40 g of TFE hadbeen fed, the vessel was vented and cooled to 25 degrees C. The THF wasthen removed under vacuum and the product was vacuum distilled at 40degrees C. to yield pure product as shown by ¹H and ¹⁹F NMR (yield 44g). Iodopropane (16.99 g) was mixed with1-(1,1,2,2-tetrafluoroethyl)imidazole (16.8 g) in dry acetonitrile (100ml), and the mixture was refluxed for 3 days. The solvent was removed invacuo, yielding a yellow waxy solid (yield 29 g). The product,1-propyl-3-(1,1,2,2-tetrafluoroethyl)imidazolium iodide was confirmed by1H NMR (in CD₃CN) [0.96 (t, 3H); 1.99 (m, 2H); 4.27 (t, 2H); 6.75 (t,1H); 7.72 (d, 2H); 9.95 (s, 1H)].

Iodide (24 g) was then added to 60 ml of dry acetone, followed by 15.4 gof potassium 1,1,2,2-tetrafluoroethanesulfonate in 75 ml of dry acetone.The mixture was heated at 60 degrees C. overnight and a dense whiteprecipitate was formed (potassium iodide). The mixture was cooled,filtered, and the solvent from the filtrate was removed using a rotaryevaporator. Some further potassium iodide was removed under filtration.The product was further purified by adding 50 g of acetone, 1 g ofcharcoal, 1 g of celite and 1 g of silica gel. The mixture was stirredfor 2 hours, filtered and the solvent removed. This yielded 15 g of aliquid, shown by NMR to be the desired product.

Example 10 Synthesis of 1-butyl-3-methylimidazolium1,1,2,3,3,3-hexafluoropropanesulfonate (Bmim-HFPS) (Cation, imidazolium;Anion, Formula 1)

1-Butyl-3-methylimidazolium chloride (Bmim-Cl, 50.0 g) and high puritydry acetone (>99.5%, 500 ml) were combined in a 1 liter flask and warmedto reflux with magnetic stirring until the solid all dissolved. At roomtemperature in a separate 1 liter flask,potassium-1,1,2,3,3,3-hexafluoropropanesulfonte (HFPS-K) was dissolvedin high purity dry acetone (550 ml). These two solutions were combinedat room temperature and allowed to stir magnetically for 12 hr underpositive nitrogen pressure. The stirring was stopped, and the KClprecipitate was allowed to settle. This solid was removed by suctionfiltration through a fritted glass funnel with a celite pad. The acetonewas removed in vacuo to give a yellow oil. The oil was further purifiedby diluting with high purity acetone (100 ml) and stirring withdecolorizing carbon (5 g). The mixture was suction filtered and theacetone removed in vacuo to give a colorless oil. This was further driedat 4 Pa and 25 degrees C. for 2 hr to provide 68.6 g of product.

¹⁹F NMR (DMSO-d₆) δ −73.8 (s, 3F); −114.5, −121.0 (ABq, J=258 Hz, 2F);−210.6 (m, J=42 Hz, 1F).

¹H NMR (DMSO-d₆) δ 0.9 (t, J=7.4 Hz, 3H); 1.3 (m, 2H); 1.8 (m, 2H); 3.9(S, 3H); 4.2 (t, J=7 Hz, 2H); 5.8 (dm, J=42 Hz, 1H); 7.7 (s, 1H); 7.8(s, 1H); 9.1 (s, 1H).

% Water by Karl-Fisher titration: 0.12%.

Analytical calculation for C₉H₁₂F₆N₂O₃S: C, 35.7: H, 4.4: N, 7.6.

Experimental Results: C, 34.7: H, 3.8: N, 7.2.

TGA (air): 10% wt. loss @ 340 degrees C., 50% wt. loss @ 367 degrees C.

TGA (N₂): 10% wt. loss @ 335 degrees C., 50% wt. loss @ 361 degrees C.

Extractable chloride by ion chromatography: 27 ppm.

Example 11 Synthesis of 1-butyl-3-methylimidazolium1,1,2-trifluoro-2-(trifluoromethoxy)ethanesulfonate (Bmim-TTES) (Cation,imidazolium; Anion, Formula 1)

1-Butyl-3-methylimidazolium chloride (Bmim-Cl, 10.0 g) and deionizedwater (15 ml) were combined at room temperature in a 200 ml flask. Atroom temperature in a separate 200 ml flask, potassium1,1,2-trifluoro-2-(trifluoromethoxy)ethanesulfonate (TTES-K, 16.4 g) wasdissolved in deionized water (90 ml). These two solutions were combinedat room temperature and allowed to stir magnetically for 30 min. underpositive nitrogen pressure to give a biphasic mixture with the desiredionic liquid as the bottom phase. The layers were separated, and theaqueous phase was extracted with 2×50 ml portions of methylene chloride.The combined organic layers were dried over magnesium sulfate andconcentrated in vacuo. The colorless oil product was dried at for 4 hrat 5 Pa and 25 degrees C. to afford 15.0 g of product.

¹⁹F NMR (DMSO-d₆) 6-56.8 (d, J_(FH)=4 Hz, 3F); −119.5, −119.9 (subsplitABq, J=260 Hz, 2F); −142.2 (dm, J_(FH)=53 Hz, 1F).

¹H NMR (DMSO-d₆) δ 0.9 (t, J=7.4 Hz, 3H); 1.3 (m, 2H); 1.8 (m, 2H); 3.9(s, 3H); 4.2 (t, J=7.0 Hz, 2H); 6.5 (dt, J=53 Hz, J=7 Hz, 1H); 7.7 (s,1H); 7.8 (s, 1H); 9.1 (s, 1H).

% Water by Karl-Fisher titration: 613 ppm.

Analytical calculation for C11H16F6N2O4S: C, 34.2: H, 4.2: N, 7.3.

Experimental Results: C, 34.0: H, 4.0: N, 7.1.

TGA (air): 10% wt. loss @ 328 degrees C., 50% wt. loss @ 354 degrees C.

TGA (N₂): 10% wt. loss @ 324 degrees C., 50% wt. loss @ 351 degrees C.

Extractable chloride by ion chromatography: <2 ppm.

Example 12 Synthesis of 1-butyl-3-methylimidazolium1,1,2-trifluoro-2-(perfluoroethoxy)ethanesulfonate (Bmim-TPES) (Cation,imidazolium; Anion, Formula 1)

1-Butyl-3-methylimidazolium chloride (Bmim-Cl, 7.8 g) and dry acetone(150 ml) were combined at room temperature in a 500 ml flask. At roomtemperature in a separate 200 ml flask, potassium1,1,2-trifluoro-2-(perfluoroethoxy)ethanesulfonate (TPES-K, 15.0 g) wasdissolved in dry acetone (300 ml). These two solutions were combined andallowed to stir magnetically for 12 hr under positive nitrogen pressure.The KCl precipitate was then allowed to settle leaving a colorlesssolution above it. The reaction mixture was filtered once through acelite/acetone pad and again through a fritted glass funnel to removethe KCl. The acetone was removed in vacuo first on a rotovap and then ona high vacuum line (4 Pa, 25 degrees C.) for 2 hr. Residual KCl wasstill precipitating out of the solution, so methylene chloride (50 ml)was added to the crude product which was then washed with deionizedwater (2×50 ml). The solution was dried over magnesium sulfate, and thesolvent was removed in vacuo to give the product as a viscous lightyellow oil (12.0 g, 62% yield).

¹⁹F NMR (CD₃CN) δ −85.8 (s, 3F); −87.9, −90.1 (subsplit ABq, J_(FF)=147Hz, 2F);

−120.6, −122.4 (subsplit ABq, J_(FF)=258 Hz, 2F); −142.2 (dm, J_(FH)=53Hz, 1F).

¹H NMR (CD₃CN) δ 1.0 (t, J=7.4 Hz, 3H); 1.4 (m, 2H); 1.8 (m, 2H); 3.9(s, 3H);

4.2 (t, J=7.0 Hz, 2H); 6.5 (dm, J=53 Hz, 1H); 7.4 (s, 1H); 7.5 (s, 1H);8.6 (s, 1H).

% Water by Karl-Fisher titration: 0.461.

Analytical calculation for C₁₂H₁₆F₈N₂O₄S: C, 33.0: H, 3.7.

Experimental Results: C, 32.0: H, 3.6.

TGA (air): 10% wt. loss @ 334 degrees C., 50% wt. loss @ 353 degrees C.

TGA (N₂): 10% wt. loss @ 330 degrees C., 50% wt. loss @ 365 degrees C.

Example 13 Synthesis of tetradecyl(tri-n-butyl)phosphonium1,1,2,3,3,3-hexafluoropropanesulfonate ([4.4.4.14]P-HFPS) (Cation,imidazolium; Anion, Formula 1)

To a 4 l round bottomed flask was added the ionic liquidtetradecyl(tri-n-butyl)phosphonium chloride (Cyphos® IL 167, 345 g) anddeionized water (1000 ml). The mixture was magnetically stirred until itwas one phase. In a separate 2 liter flask, potassium1,1,2,3,3,3-hexafluoropropanesulfonate (HFPS-K, 214.2 g) was dissolvedin deionized water (1100 ml). These solutions were combined and stirredunder positive N₂ pressure at 26 degrees C. for 1 hr producing a milkywhite oil. The oil slowly solidified (439 g) and was removed by suctionfiltration and then dissolved in chloroform (300 ml). The remainingaqueous layer (pH=2) was extracted once with chloroform (100 ml). Thechloroform layers were combined and washed with an aqueous sodiumcarbonate solution (50 ml) to remove any acidic impurity. They were thendried over magnesium sulfate, suction filtered, and reduced in vacuofirst on a rotovap and then on a high vacuum line (4 Pa, 100 degrees C.)for 16 hr to yield the final product as a white solid (380 g, 76%yield).

¹⁹F NMR (DMSO-d₆) δ −73.7 (s, 3F); −114.6, −120.9 (ABq, J=258 Hz, 2F);−210.5 (m, J_(HF)=41.5 Hz, 1F).

¹H NMR (DMSO-d₆) δ 0.8 (t, J=7.0 Hz, 3H); 0.9 (t, J=7.0 Hz, 9H); 1.3 (brs, 20H); 1.4 (m, 16H); 2.2 (m, 8H); 5.9 (m, J_(HF)=42 Hz, 1H).

% Water by Karl-Fisher titration: 895 ppm.

Analytical calculation for C29H57F6O3PS: C, 55.2: H, 9.1: N, 0.0.

Experimental Results: C, 55.1: H, 8.8: N, 0.0.

TGA (air): 10% wt. loss @ 373 degrees C., 50% wt. loss @ 421 degrees C.

TGA (N₂): 10% wt. loss @ 383 degrees C., 50% wt. loss @ 436 degrees C.

Example 14 Synthesis of Tetradecyl(tri-n-hexyl)phosphonium1,1,2-trifluoro-2-(perfluoroethoxy)ethanesulfonate ([6.6.6.14]P-TPES)(Cation, imidazolium; Anion, Formula 1)

To a 500 ml round bottomed flask was added acetone (Spectroscopic grade,50 ml) and ionic liquid tetradecyl(tri-n-hexyl)phosphonium chloride(Cyphos® IL 101, 33.7 g). The mixture was magnetically stirred until itwas one phase. In a separate 1 liter flask, potassium1,1,2-trifluoro-2-(perfluoroethoxy)ethanesulfonate (TPES-K, 21.6 g) wasdissolved in acetone (400 ml). These solutions were combined and stirredunder positive N₂ pressure at 26 degrees C. for 12 hr producing a whiteprecipitate of KCl. The precipitate was removed by suction filtration,and the acetone was removed in vacuo on a rotovap to produce the crudeproduct as a cloudy oil (48 g). Chloroform (100 ml) was added, and thesolution was washed once with deionized water (50 ml). It was then driedover magnesium sulfate and reduced in vacuo first on a rotovap and thenon a high vacuum line (8 Pa, 24 degrees C.) for 8 hr to yield the finalproduct as a slightly yellow oil (28 g, 56% yield).

¹⁹F NMR (DMSO-d₆) δ −86.1 (s, 3F); −88.4, −90.3 (subsplit ABq,J_(FF)=147 Hz, 2F); −121.4, −122.4 (subsplit ABq, J_(FF)=258 Hz, 2F);−143.0 (dm, J_(FH)=53 Hz, 1F).

¹H NMR (DMSO-d₆) δ 0.9 (m, 12H); 1.2 (m, 16H); 1.3 (m, 16H); 1.4 (m,8H);

1.5 (m, 8H); 2.2 (m, 8H); 6.3 (dm, J_(FH)=54 Hz, 1H).

% Water by Karl-Fisher titration: 0.11.

Analytical calculation for C36H69F8O4PS: C, 55.4: H, 8.9: N, 0.0.

Experimental Results: C, 55.2: H, 8.2: N, 0.1.

TGA (air): 10% wt. loss @ 311 degrees C., 50% wt. loss @ 339 degrees C.

TGA (N₂): 10% wt. loss @ 315 degrees C., 50% wt. loss @ 343 degrees C.

Example 15 Synthesis of tetradecyl(tri-n-hexyl)phosphonium1,1,2-trifluoro-2-(trifluoromethoxy)ethanesulfonate ([6.6.6.14]P-TTES)(Cation, imidazolium; Anion, Formula 1)

To a 100 ml round bottomed flask was added acetone (Spectroscopic grade,50 ml) and ionic liquid tetradecyl(tri-n-hexyl)phosphonium chloride(Cyphos® IL 101, 20.2 g). The mixture was magnetically stirred until itwas one phase. In a separate 100 ml flask, potassium1,1,2-trifluoro-2-(trifluoromethoxy)ethanesulfonate (TTES-K, 11.2 g) wasdissolved in acetone (100 ml). These solutions were combined and stirredunder positive N₂ pressure at 26 degrees C. for 12 hr producing a whiteprecipitate of KCl.

The precipitate was removed by suction filtration, and the acetone wasremoved in vacuo on a rotovap to produce the crude product as a cloudyoil. The product was diluted with ethyl ether (100 ml) and then washedonce with deionized water (50 ml), twice with an aqueous sodiumcarbonate solution (50 ml) to remove any acidic impurity, and twice morewith deionized water (50 ml). The ether solution was then dried overmagnesium sulfate and reduced in vacuo first on a rotovap and then on ahigh vacuum line (4 Pa, 24 degrees C.) for 8 hr to yield the finalproduct as an oil (19.0 g, 69% yield).

¹⁹F NMR (CD₂Cl₂) δ −60.2 (d, J_(FH)=4 Hz, 3F); −120.8, −125.1 (subsplitABq, J=260 Hz, 2F); −143.7 (dm, J_(FH)=53 Hz, 1F).

¹H NMR (CD₂Cl₂) δ 0.9 (m, 12H); 1.2 (m, 16H); 1.3 (m, 16H); 1.4 (m, 8H);1.5 (m, 8H); 2.2 (m, 8H); 6.3 (dm, J_(FH)=54 Hz, 1H).

% Water by Karl-Fisher titration: 412 ppm.

Analytical calculation for C35H69F6O4PS: C, 57.5: H, 9.5: N, 0.0.

Experimental results: C, 57.8: H, 9.3: N, 0.0.

TGA (air): 10% wt. loss @ 331 degrees C., 50% wt. loss @ 359 degrees C.

TGA (N₂): 10% wt. loss @ 328 degrees C., 50% wt. loss @ 360 degrees C.

Example 16 Synthesis of 1-ethyl-3-methylimidazolium1,1,2,2-tetrafluoro-2-(pentafluoroethoxy)sulfonate (Emim-TPENTAS)(Cation, imidazolium; Anion, Formula II)

To a 500 ml round bottomed flask was added 1-ethyl-3-methylimidazoliumchloride (Emim-Cl, 98%, 18.0 g) and reagent grade acetone (150 ml). Themixture was gently warmed (50 degrees C.) until all of the Emim-Cldissolved. In a separate 500 ml flask, potassium1,1,2,2-tetrafluoro-2-(pentafluoroethoxy)sulfonate (TPENTAS-K, 43.7 g)was dissolved in reagent grade acetone (450 ml).

These solutions were combined in a 1 liter flask producing a whiteprecipitate (KCl). The mixture was stirred at 24 degrees C. for 8 hr.The KCl precipitate was then allowed to settle leaving a clear yellowsolution above it. The KCl was removed by filtration through acelite/acetone pad. The acetone was removed in vacuo to give a yellowoil which was then diluted with chloroform (100 ml). The chloroform waswashed three times with deionized water (50 ml), dried over magnesiumsulfate, filtered, and reduced in vacuo first on a rotovap and then on ahigh vacuum line (4 Pa, 25 degrees C.) for 8 hr. The product was a lightyellow oil (22.5 g).

¹⁹F NMR (DMSO-d₆) 6-82.9 (m, 2F); −87.3 (s, 3F); −89.0 (m, 2F); −118.9(s, 2F).

¹H NMR (DMSO-d₆) δ 1.5 (t, J=7.3 Hz, 3H); 3.9 (s, 3H); 4.2 (q, J=7.3 Hz,2H);

7.7 (s, 1H); 7.8 (s, 1H); 9.1 (s, 1H).

% Water by Karl-Fisher titration: 0.17%.

Analytical calculation for C10H11N2O4F9S: C, 28.2: H, 2.6: N, 6.6

Experimental results: C, 28.1: H, 2.9: N, 6.6.

TGA (air): 10% wt. loss @ 351 degrees C., 50% wt. loss @ 401 degrees C.

TGA (N₂): 10% wt. loss @ 349 degrees C., 50% wt. loss @ 406 degrees C.

Example 17 Synthesis of tetrabutylphosphonium1,12-trifluoro-2-(perfluoroethoxy)ethanesulfonate (TBP-TPES) (Cation,phosphonium; Anion, Formula 1)

To a 200 ml round bottomed flask was added deionized water (100 ml) andtetra-n-butylphosphonium bromide (Cytec Canada Inc., 20.2 g). Themixture was magnetically stirred until the solid all dissolved. In aseparate 300 ml flask, potassium1,1,2-trifluoro-2-(perfluoroethoxy)ethanesulfonate (TPES-K, 20.0 g) wasdissolved in deionized water (400 ml) heated to 70 degrees C. Thesesolutions were combined and stirred under positive N₂ pressure at 26degrees C. for 2 hr producing a lower oily layer. The product oil layerwas separated and diluted with chloroform (30 ml), then washed once withan aqueous sodium carbonate solution (4 ml) to remove any acidicimpurity, and three times with deionized water (20 ml). It was thendried over magnesium sulfate and reduced in vacuo first on a rotovap andthen on a high vacuum line (8 Pa, 24 degrees C.) for 2 hr to yield thefinal product as a colorless oil (28.1 g, 85% yield).

¹⁹F NMR (CD₂Cl₂) δ −86.4 (s, 3F); −89.0, −90.8 (subsplit ABq, J_(FF)=147Hz, 2F);

−119.2, −125.8 (subsplit ABq, J_(FF)=254 Hz, 2F); −141.7 (dm, J_(FH)=53Hz, 1F).

¹H NMR (CD₂Cl₂) δ 1.0 (t, J=7.3 Hz, 12H); 1.5 (m, 16H); 2.2 (m, 8H); 6.3(dm, J_(FH)=54 Hz, 1H).

% Water by Karl-Fisher titration: 0.29.

Analytical calculation for C20H37F8O4PS: C, 43.2: H, 6.7: N, 0.0.

Experimental results: C, 42.0: H, 6.9: N, 0.1.

Extractable bromide by ion chromatography: 21 ppm.

Example 18 Synthesis of(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)-trioctylphosphonium1,1,2,2-tetrafluoroethanesulfonate (Cation, phosphonium; Anion, Formula1)

Trioctyl phosphine (31 g) was partially dissolved in reagent-gradeacetonitrile (250 ml) in a large round-bottomed flask and stirredvigorously. 1,1,1,2,2,3,3,4,4,5,5,6,6-Tridecafluoro-8-iodooctane (44.2g) was added, and the mixture was heated under reflux at 110 degrees C.for 24 hours. The solvent was removed under vacuum giving(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)-trioctylphosphoniumiodide as a waxy solid (30.5 g). Potassium1,1,2,2-tetrafluoroethanesulfonate (TFES-K, 13.9 g) was dissolved inreagent grade acetone (100 ml) in a separate round-bottomed flask, andto this was added(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)-trioctylphosphoniumiodide (60 g). The reaction mixture was heated at 60 degrees C. underreflux for approximately 16 hours. The reaction mixture was thenfiltered using a large frit glass funnel to remove the white KIprecipitate formed, and the filtrate was placed on a rotary evaporatorfor 4 hours to remove the acetone. The liquid was left for 24 hours atroom temperature and then filtered a second time (to remove KI) to yieldthe product (62 g) as shown by proton NMR.

Example 19 Synthesis of1-methyl-3-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)imidazolium1,1,2,2-tetrafluoroethanesulfonate (Cation, imidazolium; Anion, FormulaI)

1-Methylimidazole (4.32 g, 0.52 mol) was partially dissolved inreagent-grade toluene (50 ml) in a large round-bottomed flask andstirred vigorously. 1,1,1,2,2,3,3,4,4,5,5,6,6-Tridecafluoro-8-iodooctane(26 g, 0.053 mol) was added, and the mixture was heated under reflux at110 degrees C. for 24 hours. The solvent was removed under vacuum giving1-methyl-3-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)imidazoliumiodide (30.5 g) as a waxy solid. Potassium1,1,2,2-tetrafluoroethanesulfonate (TFES-K, 12 g) was added to reagentgrade acetone (100 ml) in a separate round-bottomed flask, and thissolution was carefully added to the1-methyl-3-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)imidazoliumiodide which had been dissolved in acetone (50 ml). The reaction mixturewas heated under reflux for approximately 16 hours. The reaction mixturewas then filtered using a large frit glass funnel to remove the white KIprecipitate formed, and the filtrate was placed on a rotary evaporatorfor 4 hours to remove the acetone. The oily liquid was then filtered asecond time to yield the product, as shown by proton NMR.

Examples 20-23 exemplify the polymerization of propanediol using theionic liquids of the invention.

Example 20 Polymerization of Propanediol

1,3-Propanediol (20 g) was placed in a three neck round bottomed flask.To this was added 1,1,2,2-tetrafluoroethanesulfonic acid (0.8 wt % inthe final solution). The ionic liquid Bmim-TFES (4 g) was also added andthe solution and contents were purged with nitrogen for two hours. Thehomogeneous solution was heated using an oil bath at 160 degrees C.under a nitrogen atmosphere. Water was slowly evolved and collected in acondenser. After approximately 9-10 hours the solution went from asingle phase to a two-phase system. Upon cooling to 75 degrees C., twophases were clearly visible. The top phase was shown via NMR to beessentially polymerized propanediol (polyol). The molecular weight (Mn)was 2907, after a reaction time of 10.5 hours. The acid and ionic liquidwere found to be essentially in the lower phase with polyol in the upperphase. The lower phase can easily be separated and recycled.

Example 21 Polymerization of Propanediol

1,3-Propanediol (20 g) was placed in a three neck round bottomed flask.To this was added 1,1,2,2-tetrafluoroethanesulfonate (0.8 wt % in thefinal solution). The ionic liquid Emim-TFES (4 g) was also added and thesolution and contents were purged with nitrogen for two hours. Thehomogeneous solution was heated using an oil bath at 160 degrees C.under a nitrogen atmosphere. Water was slowly evolved and collected in acondenser. After approximately 9-10 hours the solution went from asingle phase to a two-phase system. Upon cooling to 75 degrees C., twophases were clearly visible. The top phase was shown via NMR to beessentially polymerized propanediol (polyol). The molecular weight (Mn)was 6131, after a reaction time of 10.5 hours. The acid and ionic liquidwere found to be essentially in the lower phase with polyol in the upperphase. The lower phase can easily be separated and recycled.

Example 22 Polymerization of Propanediol with Recycling of the IonicLiquid

1,3-Propanediol (30 g) was placed in a three neck round bottomed flask.To this was added 1,1,2,3,3,3-hexafluoropropanesulfonic acid (0.15 g;0.5 wt % in the final solution). The ionic liquid Bmim-TFES (2 g) wasalso added and the solution and contents were purged with nitrogen fortwo hours. The homogeneous solution was heated using an oil bath at 160degrees C. under a nitrogen atmosphere. Water was slowly evolved andcollected in a condenser. After approximately 26 hours the solution wentfrom a single phase to a two-phase system. Upon cooling to 75 degreesC., two phases were clearly visible. The top phase was shown via NMR tobe essentially polymerized propanediol (polyol). The molecular weight(Mn) was 2613, as determined using NMR. The total unsaturated ends was30 meq/Kg. The acid and ionic liquid were found to be essentially in thelower phase with polyol in the upper phase.

A portion of the lower phase (2 g) was removed using a glass pipette.This was placed in a three neck round bottomed flask, followed by 28 gof 1,3-propanediol. The homogeneous solution was heated using an oilbath at 160 degrees C. under a nitrogen atmosphere. Water was slowlyevolved and collected in a condenser. After approximately 30 hours thesolution went from a single phase to a two-phase system. Upon cooling to75 degrees C., two phases were clearly visible. The top phase was shownby NMR to be essentially polymerized propanediol (polyol). The molecularweight (Mn) was 3108 by NMR. The total unsaturated ends was 50 meq/Kg.

Example 23 Polymerization of Propanediol

1,3-Propanediol was placed in a three neck round bottomed flask. To thiswas added 0.3 g of phosphotungstic acid (Aldrich) and 2 g of the ionicliquid Bmim-TFES; the solution and contents were purged with nitrogenfor two hours. The homogeneous solution was heated using an oil bath at160 degrees C. under a nitrogen atmosphere. Water was slowly evolved andcollected in a condenser. After approximately 24 hours the solution wentfrom a single phase to a two-phase system. Upon cooling to 75 degreesC., two phases were clearly visible. The top phase was shown by NMR tobe essentially polymerized propanediol (polyol). The molecular weight(Mn) was 4319 by NMR. The total unsaturated ends was 81 meq/Kg.

1. A composition of matter of the Formula Z⁺A⁻ wherein Z⁺ is a cation ofthe formula below:

wherein R¹, R², R³, and R⁴ are independently selected from the groupconsisting of: (i) H (ii) halogen (iii) —CH₃, —C₂H₅, or C₃ to C₂₅straight-chain, branched or cyclic alkane or alkene, optionallysubstituted with at least one member selected from the group consistingof Cl, Br, F, I, OH, NH₂ and SH; (iv) —CH₃, —C₂H₅, or C₃ to C₂₅straight-chain, branched or cyclic alkane or alkene comprising one tothree heteroatoms selected from the group consisting of O, N and S, andoptionally substituted with at least one member selected from the groupconsisting of Cl, Br, F, I, OH, NH₂ and SH; (v) C₆ to C₂₅ unsubstitutedaryl or C₆ to C₂₅ unsubstituted heteroaryl having one to threeheteroatoms independently selected from the group consisting of O, N andS; and (vi) C₆ to C₂₅ substituted aryl or C₆ to C₂₅ substitutedheteroaryl having one to three heteroatoms independently selected fromthe group consisting of O, N and S; and wherein said substituted aryl orsubstituted heteroaryl has one to three substituents independentlyselected from the group consisting of: (1) —CH₃, —C₂H₅, or C₃ to C₂₅straight-chain, branched or cyclic alkane or alkene, optionallysubstituted with at least one member selected from the group consistingof Cl, Br, F, I, OH, NH₂ and SH, (2) OH, (3) NH₂, and (4) SH; andwherein optionally at least two of R¹, R², R³, and R⁴ can together forma cyclic or bicyclic alkanyl or alkenyl group; and A⁻ is an anionselected from the group consisting of Formulae I, II and III:

wherein: R¹¹ is selected from the group consisting of: (1) halogen; (2)—CH₃, —C₂H₅ or C₃ to C₁₅ straight-chain or branched alkane or alkene,optionally substituted with at least one member selected from the groupconsisting of Cl, Br, I, OH, NH₂ and SH; (3) —OCH₃, —OC₂H₅ or C₃ to C₁₅straight-chain or branched alkoxy, optionally substituted with at leastone member selected from the group consisting of Cl, Br, I, OH, NH₂ andSH; (4) C₁ to C₁₅ straight-chain or branched fluoroalkyl, optionallysubstituted with at least one member selected from the group consistingof Cl, Br, I, OH, NH₂ and SH; (5) C₁ to C₁₅ straight-chain or branchedfluoroalkoxy, optionally substituted with at least one member selectedfrom the group consisting of Cl, Br, I, OH, NH₂ and SH; (6) C₁ to C₁₅straight-chain or branched perfluoroalkyl; and (7) C₁ to C₁₅straight-chain or branched perfluoroalkoxy;

wherein: R¹² is selected from the group consisting of: (1) —CH₃, —C₂H₅or C₃ to C₁₅ straight-chain or branched alkoxy, optionally substitutedwith at least one member selected from the group consisting of Cl, Br,I, OH, NH₂ and SH; (2) C₁ to C₁₅ straight-chain or branchedfluoroalkoxy, optionally substituted with at least one member selectedfrom the group consisting of Cl, Br, I, OH, NH₂ and SH; and (3) C₁ toC₁₅ straight-chain or branched perfluoroalkoxy; and

wherein: R¹³ is selected from the group consisting of: (1) halogen; (2)—CH₃, —C₂H₅ or C₃ to C₁₅ straight-chain or branched alkane or alkene,optionally substituted with at least one member selected from the groupconsisting of Cl, Br, I, OH, NH₂ and SH; (3) —OCH₃, —OC₂H₅ or C₃ to C₁₅straight-chain or branched alkoxy, optionally substituted with at leastone member selected from the group consisting of Cl, Br, I, OH, NH₂ andSH; (4) C₁ to C₁₅ straight-chain or branched fluoroalkyl, optionallysubstituted with at least one member selected from the group consistingof Cl, Br, I, OH, NH₂ and SH; (5) C₁ to C₁₅ straight-chain or branchedfluoroalkoxy, optionally substituted with at least one member selectedfrom the group consisting of Cl, Br, I, OH, NH₂ and SH; (6) C₁ to C₁₅straight-chain or branched perfluoroalkyl; and (7) C₁ to C₁₅straight-chain or branched perfluoroalkoxy.
 2. The composition of claim1 wherein the anion is 1,1,2,2-tetrafluoroethanesulfonate;2-chloro-1,1,2-trifluoroethanesulfonate;1,1,2,3,3,3-hexafluoropropanesulfonate;1,1,2-trifluoro-2-(trifluoromethoxy)ethanesulfonate;1,1,2-trifluoro-2-(pentafluoroethoxy)ethanesulfonate;2-(1,2,2,2-tetrafluoroethoxy)-1,1,2,2-tetrafluoroethanesulfonate;2-(1,1,2,2-tetrafluoroethoxy)-1,1,2,2-tetrafluoroethanesulfonate;2-(1,1,2,2-tetrafluoro-2-iodoethoxy)-1,1,2,2-tetrafluoroethanesulfonate;1,1,2,2-tetrafluoro-2-(pentafluoroethoxy)ethanesulfonate;N,N-bis(1,1,2,2-tetrafluoroethanesulfonyl)imide; orN,N-bis(1,1,2,3,3,3-hexafluoropropanesulfonyl)imide.